Density functional theory computational study on the thermal cycloreversion of 2-acetoxy-2-methoxy-5,5-dimethyl-Delta3-1,3,4-oxadiazoline: evidence for a carbonyl ylide intermediate.

doi:10.1021/JO0511750

Paper

Density functional theory computational study on the thermal cycloreversion of 2-acetoxy-2-methoxy-5,5-dimethyl-Delta3-1,3,4-oxadiazoline: evidence for a carbonyl ylide intermediate.

Published Sep 22, 2005 · W. Czardybon, J. Warkentin, N. H. Werstiuk

The Journal of organic chemistry

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4

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Abstract

Three [3 + 2] cycloreversions of 2-acetoxy-2-methoxy-5,5-dimethyl-Delta(3)-1,3,4-oxadiazolines were examined by computation at the density functional level of theory. The lowest activation energies are those for cycloreversion to 2-diazopropane and acetic methylcarbonic anhydride and for cycloreversion to N(2) and a carbonyl ylide. Those are the reactions that are observed experimentally. A third cycloreversion, to acetoxy(methoxy)diazomethane and acetone, has a much larger barrier. The carbonyl ylide is a real intermediate, but it fragments easily to acetone and acetoxy(methoxy)carbene. The lifetime of the ylide may be so short, in some cases, as to blur the distinction between a two-step cycloreversion of the oxadiazoline and a concerted process that generates three fragments in one step.

Study Snapshot

The cycloreversion of 2-acetoxy-2-methoxy-5,5-dimethyl-Delta(3)-1,3,4-oxadiazoline to 2-diazopropane and acetic methylcarbonic anhydride is the most efficient, with a carbonyl

PopulationOlder adults (50-71 years)

Sample size24

MethodsObservational

OutcomesBody Mass Index projections

ResultsSocial networks mitigate obesity in older groups.

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Density functional theory computational study on the thermal cycloreversion of 2-acetoxy-2-methoxy-5,5-dimethyl-Delta3-1,3,4-oxadiazoline: evidence for a carbonyl ylide intermediate.

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